Herbicidal propylene oxide derivatives

ABSTRACT

This invention relates to herbicidally active propylene oxide derivatives, agriculturally suitable compositions thereof, and a method of using them as herbicides or plant growth regulants.

RELATED U.S. APPLICATION

This is a continuation-in-part of U.S. Ser. No. 699,526 filed Feb. 8, 1985, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to herbicidally active propylene oxide compounds, agriculturally suitable compositions thereof and a method of using the compounds and the compositions as general or selective preemergent and/or post-emergent herbicides or plant growth regulants.

In the most common situation, the control of undesired vegetation is desired to permit the growth of useful crops such as cotton, rice, corn, wheat and soybeans, to name a few. Unchecked weed growth in such useful crops can cause significant losses, reducing profit to the farmer and increasing costs to the consumer. In other situations, herbicides are desired which will control all plant growth. Examples of areas in which complete control of all vegetation is desired are areas around fuel storage tanks, ammunition depots and industrial storage areas. There are many products commercially available for these purposes, but the search continues for products which are more effective, less costly and environmentally safe.

Herbicidal compounds which exhibit sufficient selectivity, that is, which will control the growth of undesired vegetation but which will not damage useful crop plants are difficult to find. Even though there are herbicides which exhibit excellent selectivity on a number of crops while still controlling weeds at very low application rates there is a need to provide greater protection for crop plants than that provided by herbicides already disclosed. Propylene oxide derivatives of formula: ##STR1## where R is CH₃ or phenyl, are described by H. Haubenstock and W. Naegele in Makromol. Chem., 97, 248 (1966). This article discusses the cationic polymerization of epoxides, but does not disclose any herbicidal utility for these compounds.

U.S. Pat. No. 4,211,549 discloses substituted oxirane compounds of formula ##STR2## where R is Cl, Br or CH₃, and their use as herbicides.

Compounds of formula ##STR3## are described by D. V. Gardner, et al., J. Med. Chem., 22, 1373 (1979) and in British Pat. No. 1,448,437 (published Sept. 8, 1976), as intermediates in the synthesis of certain CNS-antidepressant agents.

SUMMARY OF THE INVENTION

The present invention relates to compounds of the formula ##STR4## wherein R¹ is ##STR5## where R³, R⁴, R₁ ³ and R₁ ⁴ are independently H, F, Cl, Br, CF₃, CN, NO₂, OCH₂ CH₂ OCH₃, C₁ -C₃ alkyl, C₁ -C₃ haloalkyl, C₁ -C₃ alkoxy, C₁ -C₃ haloalkoxy, C₁ -C₃ alkylthio, or C₁ -C₃ haloalkylthio; and

R⁵ is H, Cl or CH₃ ;

R² is C₂ -C₄ alkyl, C₃ -C₆ cycloalkyl, ##STR6## where R₁ ³, R₁ ⁴, and R⁵ are as previously defined;

X is F, CH₃, or OR⁶ ;

X¹ is H, F, CH₃, or OR⁶ ;

where

R⁶ is H, C₁ -C₃ alkyl, C(O)CH₃ or C(O)NHCH₃ ; and

L is C(O), CH₂, CH₂ CH₂, or CH₂ CH₂ CH₂.

The compounds of the invention are useful as general or selective preemergent and/or postemergent herbicides or plant growth regulants. The compounds of the invention are particularly useful for the control of weeds in rice.

Compounds that are preferred for reasons of increased ease of synthesis and/or greater herbicidal efficacy are:

(1) Compounds of Formulae I, II, and III where both of R¹ and R² are independently aryl or thienyl, R³, R⁴, R₁ ³ and R₁ ⁴ are independently H, F, Cl, Br, CF₃, CN, OCH₂ CH₂ OCH₃, C₁ -C₃ alkyl, C₁ -C₃ haloalkyl, C₁ -C₃ alkoxy, C₁ -C₃ haloalkoxy, C₁ -C₃ alkylthio, or C₁ -C₃ haloalkylthio substituted at the 3 or 4 position, and L is CH₂ or C(O).

(2) Compounds of Preferred 1 where R³, R⁴, R₁ ³ and R₁ ⁴ are independently H, F, Cl, CF₃, C₁ -C₃ alkoxy, or C₁ -C₃ alkyl and X and X¹ are OH or OCH₃.

Specifically preferred for reasons of greatest ease of synthesis or highest herbicidal activity or both are:

1. 2-[1-(4-chlorophenyl)-2-methylpropyl]oxirane

2. α,α-bis(4-chlorophenyl)-2-oxiranemethanol

3. α-phenyl-α-[3-(trifluoromethyl)phenyl]oxiranemethanol

4. α-(4-chlorophenyl)-α-(3-thienyl)oxiranemethanol

5. α-(4-chlorophenyl)-α-phenyloxiranemethanol

6. α,α-bis(4-fluorophenyl)-2-oxiranemethanol

7. 3-(4-fluorophenyl)-3-oxiranyl-1(3H)isobenzofuranone

8. 1-(4-fluorophenyl)-1,3-dihydro-1-oxiranyl-(R)-isobenzofuran

9. α-(4-chlorophenyl)-α-(3,5-dichlorophenyl)oxiranemethanol

Another embodiment of the invention are compounds of the formula ##STR7## wherein R¹ is ##STR8## R² is C₂ -C₄ alkyl, C₃ -C₆ cycloalkyl, or ##STR9## where R³, R⁴, R₁ ³ and R₁ ⁴ are independently H, F, Cl, Br, CF₃, OCH₂ CH₂ OCH₃, C₁ -C₃ alkyl, C₁ -C₃ haloalkyl, C₁ -C₃ alkoxy, or C₁ -C₃ alkylthio;

X is OR⁶ ; and

R⁶ is H, C₁ -C₃ alkyl or C(O)CH₃.

This invention also pertains to agriculturally suitable compositions containing mixture of the compounds of Formulae I, II, or III with Compound IVa or IVb, and their method-of-use for controlling weeds in rice.

Preferred for reasons of increased ease of synthesis, greater herbicidal activity or better selectivity or both is the combination of specifically preferred compounds 2, 3, 4, 5, 7, 8 and 9 and 2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoic acid, methyl ester (IVa) or N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1-methyl-4-ethoxycarbonyl-5-pyrazolesulfonamide (IVb) shown below: ##STR10##

The combinations of IVa or IVb with the compounds of the present invention provide especially good results when used in growing rice.

This invention further pertains to agriculturally suitable compositions containing the compounds of Formulae I, II, and III and their method-of-use for controlling grasses in wheat. Preferred for reasons of increased ease of synthesis, greater herbicidal activity or better selectivity or both is specifically preferred compound 6.

Synthesis

Most of the compounds of Formula I may be prepared by the action of an organic peracid, such as m-chloroperbenzoic acid, on a substituted propene of Formula V, as shown in Equation 1. ##STR11## wherein R=alkyl or aryl, especially 3-ClC₆ H₄, and X, R¹ and R² are as previously defined, provided that R³, R⁴, R₁ ³, R₁ ⁴ and R⁵ are neither alkylthio nor haloalkylthio.

The reaction of Equation 1 is best conducted in an inert solvent such as dichloromethane at 0° to 40° C. for 1-48 hours. The product may be isolated by destroying excess peracid with aqueous sodium bisulfite, washing out the acidic by-products with aqueous sodium bicarbonate, and evaporation of solvent. Purification may be achieved by crystallization or chromatography of the residue.

The compounds of Formula V may be prepared by several methods, including those outlined in Equation 2. ##STR12## wherein R¹ and R² are as defined in the Summary of the Invention, R⁶ is C₁ -C₃ alkyl, and M is MgBr, MgCl or Li.

The reaction of Equation 2(a) is well known in the art, and involves the addition of one equivalent of vinylmagnesium halide (i.e., bromide or chloride) or vinyllithium to an appropriately substituted benzophenone of Formula VI. The crude product is usually of suitable purity for the next process.

Compounds of Formula Va, wherein R¹ and R² are halophenyl, are also herbicidal.

The reaction of Equation 2(b) may be conducted by contacting a compound of Formula Va in an aprotic, polar solvent such as DMF with one equivalent of a strong base, such as sodium hydride, and an excess of a lower alkyl iodide or sulfate at 25°-80° C. The product may be isolated by dilution with ice-water and extraction with a nonpolar organic solvent, such as ether or pentane, and may be purified by chromatography.

The reaction of Equation 2(c) between the disubstituted acetaldehyde of Formula VII and methylene triphenylphosphorane may be performed as described by G. Wittig and U. Schoellkopf, in Org. Syn., 40, 66 (1960). The crude reaction product may be purified by chromatography or distillation.

Certain compounds of Formula I may be obtained by the action of a sulfonium or sulfoxonium methylide on the appropriate aldehyde of Formula VIII. This method, shown in Equation 3, would be useful in the preparation of sulfur-containing propylene oxide derivatives. ##STR13## wherein R¹ and R² are as defined in the Summary of the Invention, and X is H, OH, or C₁ -C₃ alkoxy.

The reaction of Equation 3 may be carried out according to the conditions described by T. Kutsuma, et al., in Heterocycles, 8, 397 (1977), or by the more traditional methods referenced therein.

The compounds of Formula VIII, wherein X is H, are well-known in the art. Others may be prepared according to the teachings of K. Ogura and G. Tsuchihashi, Tetrahedron Lett., 2681 (1972); E. L. Eliel, et al., J. Am. Chem. Soc., 100, 1615 (1978); or T. Mukaiyama et al., Chem. Lett., 1253 (1978).

Other compounds of Formula I may be prepared by the action of an acylating agent on an alcohol of Formula Ia, as shown in Equation 4. ##STR14## wherein R¹ and R² are as previously defined.

The reaction of Equaion 4(a) may be performed using an acetylation catalyst such as 4-dimethylaminopyridine according to W. Steglich and G. Hofle, Angew. Chem., Int. Ed., 8, 981 (1969). The reaction of Equation 4(b) is performed using methyl isocyanate and di-n-butyltin dilaurate as a catalyst optionally in a solvent for 1-3 days at 25° to 60° C. The crude products Ib or Ic may be purified by crystallization or chromatography. The reaction of Equation 4(c) may be carried out by adding 0.9 to 1.1 mole-equivalents of diethylamino sulfur trifluoride to a solution of Ia in dichloromethane at -30° to 20° C., washing the reaction mixture with aqueous NaHCO₃, and concentration. If necessary, the crude product, Id, may be purified by chromatography.

Another method by which compounds of Formulat Ia may be prepared is the reaction of a lithioarene of Formula X with an α,β-epoxyketone of Formula XI, as shown in Equation 5. The ketones may be prepared as described for 4'-methoxy-2,3-epoxypropiophenone (A. P. Beracierta and D. A. Whiting, J. Chem. Soc. Perkin 1, 1978, 1257.) ##STR15##

The reaction of Equation 5(a) is conducted by cooling a solution of an arylbromide in an ethereal solvent such as tetrahydrofuran to -78° to -110° C. and adding 0.9 to 1.1 equivalents of a solution of n-butyllithium in an inert solvent such as hexane. In the same flask, the reaction of Equation 5(b) is performed by adding a solution of the appropriate epoxy-ketone XI in an ethereal solvent such as tetrahydrofuran and allowing the reaction mixture to warm to 0° to 25° C. for 0.1 to 1 hour. The product may be isolated by quenching with a weak acid such as aqueous ammonium chloride, extraction, concentration, and trituration or chromatography.

The compounds of Formula II may be prepared by direct analogy with the methods described for those of Formula I in Equations 1, 2, 3 and 4, starting with the appropriately substituted dibenzocycloheptadienones.

Compounds of Formula III may be prepared by the methods outlined in Equations 6 and 7. ##STR16## wherein R, R¹, R₁ ³, and R₁ ⁴ are as defined in Equation 1, n is 1 or 2, and M is MgBr, MgCl or Li.

In the reaction of Equation 6a, an appropriately substituted phthalide (n=1) or dihydroisochromanone (n=2) is contacted in an ethereal solvent with one equivalent of an aryl Grignard or lithium reagent at low temperatures (-78° to 0° C.). The reaction product may be isolated by standard procedures, or the reaction mixture may be directly contacted with one equivalent of a vinyl lithium or a vinyl Grignard solution. The product may be isolated after reaction at 0°-50° C. by the addition of aqueous NH₄ Cl and extraction into an organic solvent. Purification may be achieved by crystallization or chromatography to afford the compounds of Formula XIII. Cyclization to the compounds of Formula XIV may be performed by contacting a mixture of one equivalent of XIII with 1.1-1.5 equivalents of triphenylphosphine in an inert solvent such as dichloromethane or THF, and adding 1.1-1.5 equivalents of diethylazodicarboxylate. After 1-20 hours, the reaction mixture may be filtered through silica gel to provide the cyclic ethers of Formula XIV as a mixture of diastereomers, which may then be oxidized as described for Equation 1. The resulting epoxide mixture may then be separated by silica gel chromatography, or may be utilized as such.

Other compounds of Formula III may be prepared from the corresponding 2-aroylbenzoic acids as outlined in Equation 7. ##STR17## wherein R, R¹, R₁ ³ and R₁ ⁴ are as defined in Equation 1, and M=MgBr, MgCl or Li.

The reaction of Equation 7a may be carried out by adding 2.0 to 2.5 equivalents of the vinyl Grignard or vinyl lithium solution to the appropriate ketone of Formula XV in an ethereal solvent such as THF at -20 ° to 35°. After the reaction mixture is acidified with aqueous mineral acid, the product of Formula XVI may be isolated by extraction into an organic solvent and concentration. The reaction of Equation 7b may be performed as described for that of Equation 1. Alternatively, the phthalide of Formula XVI may be reduced to the diol of Formula XVII by a hydride donor such as lithium aluminum hydride. This reaction may be conducted by adding 0.5 to 1 mole-equivalents of the reagent to XVI in a solvent such as diethyl ether at -20° to 20°, stirring for 0.1 to 1 hour, adding aqueous NaOH to precipitate inorganic salts, and filtration. The compound of Formula XVII may be isolated by evaporation of the solvent. The reactions of Equations 7d and 7e are then performed as described for those of Equations 6b and 6c, respectively. 2-[[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoic acid, methyl ester is a known herbicide and may be synthesized according to the methods taught in U.S. Pat. No. 4,420,325 (issued Dec. 13, 1983), which is herein incorporated by reference.

N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-1-methyl-4-ethoxycarbonyl-5-pyrazolesulfonamide is a known herbicide and may be synthesized according to the methods taught in EP-A No. 95,925 (published Dec. 7, 1983), which is herein incorporated by reference.

One skilled in the art will recognize that many of the compounds of Formulae I, II, and III can contain up to two asymmetric carbon atoms (e.g., when R¹ ≠R²). The resulting diastereoisomers both possess herbicidal utility and their separation is optional.

The following examples further illustrate the preparation of compounds of Formulae I, II and III. Unless otherwise noted, temperatures are reported in degrees Celsius.

EXAMPLE 1 3-p-Chlorophenyl-4-methyl-1-pentene

To a solution of 10.0 g of 4-chloro-α-[2-methylethyl]benzeneacetonitrile in 100 mL of tetrahydrofuran was added 55 mL of 1M diisobutylaluminum hydride in toluene. The reaction mixture was stirred for 2 hours at 25°, cooled to 0°, and treated with 1 mL of methanol, then 40 mL of 10% aqueous HCl. The mixture was extracted with 100 mL of ether, washed with brine, dried (MgSO₄), and concentrated to dryness. The crude product (a 2:1 mixture of aldehyde and starting nitrile) was used in the next step. The mixture was dissolved in ether and added to methylene triphenylphosphorane (prepared by adding 28 mL of 1.6M n-butyllithium in hexane to 16 g of methyl triphenylphosphonium bromide in 150 mL of ether at 0°). The reaction mixture was stirred at 25° overnight, quenched with 2 mL of absolute EtOH, and filtered. The filtrate was washed with water, brine, dried (MgSO₄), and concentrated. The residue was "chromatographed" on silica gel; elution with hexane provided 4.6 g of the title compound.

NMR (CDCl₃): δ0.7 (d, 3H), 0.95 (d, 3H), 1.9 (m, 1H), 2.9 (t, 1H), 4.9-6.2 (m, 3H), 7.3 (AB quartet, 4H).

EXAMPLE 2 2-[1-(4-Chlorophenyl)-2-methylpropyl]oxirane

A mixture of 4 g of the product of Example 1 and 4.5 g of m-chloroperbenzoic acid in 50 mL of chloroform was stirred overnight at room temperature and filtered. The filtrate was washed with aqueous NaHSO₃, aqueous NaHCO₃, brine, dried (Na₂ SO₄), and concentrated. The residue was a mixture of diastereomeric epoxides.

NMR (CDCl₃): δ0.8 (d of d, 3H) 1.1 (two d of d, 3H), 2.0 (m, 1H), 2.4-3.0 (m), 3.2 (m, 1H), 7.3 (m, 4H).

EXAMPLE 3 α,α-bis(4-Chlorophenyl)oxiranemethanol

To a solution of 6 g of 4,4'-dichlorobenzophenone in 200 mL of ether was added 30 mL of 1.4M vinylmagnesium bromide/THF at 0°. After being stirred at 25° for 20 minutes, the mixture was poured onto aqueous NH₄ Cl, partitioned, washed with brine, dried (MgSO₄), filtered, and concentrated. The crude adduct was allowed to stand in 50 mL of methylene chloride with 5.8 g of m-chloroperbenzoic acid for 3 days at 25°. The mixture was diluted with CH₂ Cl₂, washed with aqueous NaHSO₃, aqueous NaHCO₃, brine, dried (Na₂ SO₄), concentrated, and chromatographed (150 mL SiO₂ /30% CH₂ Cl₂ in hexane) to provide 2.9 g of the title compound (after washing the concentrated fractions with pentane), m.p. 87°-88°.

NMR (CDCl₃): δ2.7 (s, 1H), 2.8 (m, 1H), 2.9 (m, 1H), 3.7 (m, 1H), 7.4 (m, 8H).

EXAMPLE 4 (α,α-bis(4-Fluorophenyl)-2-oxiranyl)methyl acetate

To a solution of 0.7 g of α,α-bis(4-fluorophenyl)oxiranemethanol (prepared as described above for the chloro analog) in 1 mL of triethylamine and 1 mL of acetic anhydride was added 50 mg of 4-dimethylaminopyridine. The mixture was allowed to stand at 25° for 3 days, partitioned between ether and water, washed with aqueous NaHCO₃, aqueous oxalic acid, aqueous NaHCO₃, brine, dried (MgSO₄), and concentrated. The residue was chromatographed and triturated with pentane to provide 0.7 g of the title compound, m.p. 88°-90°.

NMR (CDCl₃): δ2.1 (d of d, 1H), 2.2 (2, 3H), 2.8 (t, 1H), 4.5 (d of d, 1H), 7.0 (d of t, J=2, 9 Hz), 7.35 (d of d, J=6, 9 Hz).

EXAMPLE 5 α-(4-Chlorophenyl)-α-(2-fluorophenyl)oxiranemethanol

To a solution of 0.9 g of 2-bromofluorobenzene in 10 mL of THF and 20 mL of diethyl ether was added 3.2 mL of a 1.6M solution of n-butyllithium in hexanes at -78°. After the addition was complete, a solution of 0.9 g of 4'-chloro-2,3-epoxypropiophenone (J.T. Lumb, Tetrahedron Lett., 1970, 579) in 5 mL of ether was added, and the reaction mixture was allowed to warm to room temperature. After being quenched with 10 mL of saturated NH₄ Cl (aqueous), the mixture was separated, the organic phase was washed with brine, dried (MgSO₄), filtered, concentrated, and triturated with hexanes to afford 1.0 g of the title compound, m.p. 120°-122°.

NMR (CDCl₃): δ2.81 (s, 1H), 2.88 (t, 1H), 3.03 (d of d, 1H), 3.87 (m, 1H), 7.0 (d of d, 1H), 7.32 (m, 6H), 7.78 (d of t, 1H).

Using the procedures described in Equations 1-7 and Examples 1-5 above, one skilled in the art can prepare the compounds shown in Tables 1-5.

    ______________________________________                                         Table of Structures                                                            ______________________________________                                         General Structure 1                                                                          ##STR18##                                                        General Structure 2                                                                          ##STR19##                                                        General Structure 3                                                                          ##STR20##                                                        General Structure 4                                                                          ##STR21##                                                        General Structure 5                                                                          ##STR22##                                                        ______________________________________                                    

                                      TABLE 1                                      __________________________________________________________________________     General Structure I                                                            Cmpd.                                                                          No. R.sup.2                                                                               R.sup.3   R.sup.4                                                                               X     m.p.(°C.)                             __________________________________________________________________________      1  CH.sub.3                                                                              4-Cl      H      OH    59-61 (isomer A)                              2  CH.sub.3                                                                              4-Cl      H      OH    oil (1:1 mixture                                                               of isomers)                                   3  CH.sub.3                                                                              4-F       H      OH                                                  4  CH.sub.3                                                                              3-F       4-F    OH                                                  5  CH.sub.3                                                                              4-CF.sub.3                                                                               4-F    OH                                                  6  CH.sub.3                                                                              3-CN      4-F    H                                                   7  CH.sub.3                                                                              3-Cl      4-F    OH                                                  8  C.sub.2 H.sub.5                                                                       3-Cl      4-F    H                                                   9  C.sub.2 H.sub.5                                                                       4-F       4-F    OH                                                 10  C.sub.2 H.sub.5                                                                       4-CH.sub.3                                                                               4-F    OH                                                 11  C.sub.2 H.sub.5                                                                       4-CN      4-F    OH                                                 12  C.sub.2 H.sub.5                                                                       3-F       4-OCH.sub.2 CH.sub.3                                                                  OH                                                 13  C.sub.2 H.sub.5                                                                       3-CF.sub.3                                                                               H      OH                                                 14   -n-C.sub.3 H.sub.7                                                                   3-Cl      H      OH                                                 15   -n-C.sub.3 H.sub.7                                                                   3-F       H      H                                                  16   -n-C.sub.3 H.sub.7                                                                   4-F       H      OCH.sub.3                                          17   -n-C.sub.3 H.sub.7                                                                   4-Br      H      OH                                                 18   -n-C.sub.3 H.sub.7                                                                   4-CF.sub.3                                                                               H      OCOCH.sub.3                                        19   -n-C.sub.3 H.sub.7                                                                   4-OCF.sub.3                                                                              H      OH                                                 20   .sub.-i-C.sub.3 H.sub.7                                                              4-Cl      H      H     oil                                          21   .sub.-i-C.sub.3 H.sub.7                                                              4-Cl      H      OH    75-76.5 (isomer A)                           22   .sub.-i-C.sub.3 H.sub.7                                                              4-Cl      H      OH    73-74 (isomer B)                             23   .sub.-i-C.sub.3 H.sub.7                                                              4-Cl      H      OCH.sub.3                                          24   .sub.-i-C.sub.3 H.sub.7                                                              4-OCH.sub.3                                                                              H      H     oil                                          25   .sub.-i-C.sub.3 H.sub.7                                                              3-Cl      H      H                                                  26   .sub.-i-C.sub.3 H.sub.7                                                              2-Cl      H      H     oil                                          27   .sub.-i-C.sub.3 H.sub.7                                                              3-Cl      H      OH                                                 28   .sub.-i-C.sub.3 H.sub.7                                                              3-CH.sub.3                                                                               4-F    OH                                                 29   .sub.-i-C.sub.3 H.sub.7                                                              3-F       H      OH                                                 30   .sub.-i-C.sub.3 H.sub.7                                                              4-F       H      OH                                                 31   .sub.-i-C.sub.3 H.sub.7                                                              H         H      OH                                                 32   .sub.-i-C.sub.3 H.sub.7                                                              H         H      H     oil                                          33   -n-C.sub.4 H.sub.9                                                                   4-Cl      H      OH                                                 34   -n-C.sub.4 H.sub.9                                                                   4-F       H      OH    53-54                                        35   -n-C.sub.4 H.sub.9                                                                   3-F       H      H                                                  36   -n-C.sub.4 H.sub.9                                                                   3-Cl      H      OH                                                 37   .sub.-i-C.sub.4 H.sub.9                                                              4-OCF.sub.3                                                                              H      OH                                                 38   .sub.-i-C.sub.4 H.sub.9                                                              3-CF.sub.3                                                                               H      OH                                                 39   .sub.-i-C.sub.4 H.sub.9                                                              3-CH.sub.2 CH.sub.3                                                                      4-F    OH                                                 40   .sub.-i-C.sub.4 H.sub.9                                                              4-F       H      OH                                                 41   .sub.-i-C.sub.4 H.sub.9                                                              3-Cl      H      OH                                                 42   .sub.-i-C.sub.4 H.sub.9                                                              4-CN      H      OH                                                 43   .sub.-s-C.sub.4 H.sub.9                                                              2-F       H      OH                                                 44   .sub.-s-C.sub.4 H.sub.9                                                              3-F       H      OCH.sub.3                                          45   .sub.-s-C.sub.4 H.sub.9                                                              4-Br      H      OH                                                 46   .sub.-s-C.sub.4 H.sub.9                                                              H         H      OH                                                 47   .sub.-s-C.sub.4 H.sub.9                                                              3-OCH.sub.3                                                                              H      OH                                                 48   .sub.-t-C.sub.4 H.sub.9                                                              4-SCH.sub.3                                                                              H      OH                                                 49   .sub.-t-C.sub.4 H.sub.9                                                              3-F       4-F    OH                                                 50   .sub.-t-C.sub.4 H.sub.9                                                              4-OCH.sub.2 CH.sub.2 OCH.sub.3                                                           H      OH                                                 51   .sub.-t-C.sub.4 H.sub.9                                                              4-Cl      H      OH    110-118                                      52  cyclopropyl                                                                           3-Cl      H      OH                                                 53  cyclopropyl                                                                           3-F       H      OH                                                 54  cyclopropyl                                                                           3-CN      H      OH                                                 55  cyclobutyl                                                                            4-Cl      3-Cl   OH                                                 56  cyclobutyl                                                                            4-F       H      OH                                                 57  cyclobutyl                                                                            3-Cl      H      OH                                                 58  cyclopentyl                                                                           3-F       H      OH                                                 59  cyclopentyl                                                                           4-F       H      H                                                  60  cyclopentyl                                                                           4-SCHF.sub.2                                                                             H      OH                                                 61  cyclopentyl                                                                           4-CF.sub.3                                                                               H      OH                                                 62  cyclopentyl                                                                           3-Cl      5-Cl   OH                                                 63  cyclohexyl                                                                            3-CF.sub.3                                                                               H      OH                                                 64  cyclohexyl                                                                            3-F       H      OH                                                 65  cyclohexyl                                                                            4-Cl      H      OH                                                 66  cyclohexyl                                                                            4-OCF.sub.3                                                                              H      OH                                                 __________________________________________________________________________

                  TABLE 2                                                          ______________________________________                                         General Structure 1                                                            Cmpd.                                     m.p.                                 No.   R.sup.2 R.sup.3                                                                              R.sup.4 X       R.sup.5                                                                              (°C.)                         ______________________________________                                         67    2-thienyl H   H       OH      H                                          68    2-thienyl 4-F H       OH      H                                          69    2-thienyl 4-Cl                                                                               H       OH      H     105-                                                                           105.5                                70    2-thienyl 3-F H       OH      H                                          71    2-thienyl 3-F 4-F     H       H                                          72    2-thienyl 3-CH.sub.3                                                                         H       OH      H                                          73    2-thienyl 3-Cl                                                                               H       OH      H                                          74    3-thienyl H   H       OH      H                                          75    3-thienyl 4-CF.sub.3                                                                         H       OH      H                                          76    3-thienyl 3-F H       OH      H                                          77    3-thienyl 4-F H       OCH.sub.3                                                                              H                                          78    3-thienyl 4-Cl                                                                               H       OH      H     106-                                                                           107                                  79    3-thienyl 3-Cl                                                                               H       OH      H                                          80    3-thienyl 3-CN                                                                               H       OH      H                                          81    3-thienyl 3-CH.sub.2 CH.sub.3                                                                H       OH      H                                          82    2-thienyl 3-F H       OH      5-Cl  81-                                                                            81.5                                 83    2-thienyl 4-F H       OH      5-Cl                                       84    2-thienyl 3-Cl                                                                               5-Cl    OH      5-Cl                                       85    2-thienyl H   H       OH      5-CH.sub.3                                 86    2-thienyl 4-OCH.sub.3                                                                        H       OH      5-CH.sub.3                                 87    2-thienyl 4-SCH.sub.3                                                                        H       OH      5-CH.sub.3                                 88    2-thienyl 3-CN                                                                               H       OH      3-CH.sub.3                                 89    2-thienyl 3-CF.sub.3                                                                         H       OH      5-CH.sub.3                                 90    2-thienyl 4-F H       OH      5-CH.sub.3                                 91    3-thienyl 4-F H       OH      5-CH.sub.3                                 92    3-thienyl 4-F H       OCOCH.sub.3                                                                            4-Cl                                       93    3-thienyl 3-F 3-CF.sub.3                                                                             OH      4-Cl                                       94    3-thienyl 3-Cl                                                                               H       OH      4-Cl                                       95    3-thienyl 3-Cl                                                                               H       OCH.sub.3                                                                              4-Cl                                       96    3-thienyl 3-Cl                                                                               H       OH      2-Cl                                       97    3-thienyl 3-Cl                                                                               H       OCOCH.sub.3                                                                            2-Cl                                       98    3-thienyl 3-Cl                                                                               H       OCH.sub.3                                                                              2-Cl                                       99    3-thienyl 3-Cl                                                                               H       OH      4-CH.sub.3                                 ______________________________________                                    

                                      TABLE 3                                      __________________________________________________________________________     General Structure 2                                                            Cmpd.                                                                          No. R.sup.3                                                                             R.sup.4                                                                            R.sub.1.sup.3                                                                           R.sub.1.sup.4                                                                      X      m.p.(°C.)                              __________________________________________________________________________     100 4-F  H   2'-F     H   OH     97-102                                        101 4-F  H   4'-F     H   CH.sub.3                                                                              oil                                           102 4-F  H   4'-F     H   OCH.sub.3                                                                             oil                                           103 4-F  H   4'-CF.sub.3                                                                             H   OH     101-102.5                                     104 4-F  H   4'-OCH.sub.3                                                                            H   OH     97-98.5                                       105 4-F  H   4'-SCH.sub.3                                                                            H   OH     108-110                                       106 4-F  H   3'-CN    H   OH     86-90                                         107 4-F  H   4'-Br    H   OH     89-91                                         108 4-F  H   3'-Cl    5'-Cl                                                                              OH     127-128.5                                     109 4-F  H   3'-CF.sub.3                                                                             H   OH     98-98.5                                       110 4-F  H   2'-F     5'-F                                                                               OH     136-140                                       111 4-F  H   4'-CH.sub.3                                                                             H   OH     84-85                                         112 4-F  H   3'-CH.sub.3                                                                             H   OH     81-82.5                                       113 4-F  H   2'-CH.sub.3                                                                             H   OH     131-132                                       114 4-F  H   4'-F     H   H      oil                                           115 4-F  H   4'-Cl    H   OH     104-106                                       116 4-F  H   3' -CF.sub.3                                                                            5'-CF.sub.3                                                                        OH     83-84                                         117 4-F  H   3'-F     4'-F                                                                               OH     91-92                                         118 4-F  H   3'-Cl    H   OH     88                                            119 4-F  H   4'-F     H   F      oil                                           120 4-F  H   4'-F     H   OH     145-147                                       121 4-F  H   4'-F     H   OCOCH.sub.3                                                                           88-90                                         122 4-F  H   3'-Cl    4'-Cl                                                                              OH                                                   123 4-F  H   H        H   OH                                                   124 4-F  H   H        H   OCH.sub.3                                            125 4-F  3-CH.sub.3                                                                         3'-Cl    4'-F                                                                               OH                                                   126 4-F  H   3'-F     H   OCH.sub.3                                            127 4-F  H   3'-Cl    H   OCOCH.sub.3                                          128 4-F  H   3'-CH.sub.3                                                                             H   OCH.sub.3                                            129 4-F  H   3'-CN    H   OCOCH.sub.3                                          130 4-F  H   2'-F     3'-F                                                                               OCOCH.sub.3                                          131 4-F  H   3'-F     4'-F                                                                               OCONHCH.sub.3                                        132 4-F  H   4'-Cl    H   OCH.sub.3                                            133 3-F  H   3'-F     H   OH     117-119                                       134 3-F  H   4'-F     H   OH     86-87                                         135 3-F  H   3'-CN    H   OH     119-121.5                                     136 3-F  H   3'-F     4'-F                                                                               OH     86-89                                         137 3-F  4-F 3'-F     4'-F                                                                               OH     96-97                                         138 3-F  H   3'-F.sub.3 C                                                                            H   OH     oil                                           139 3-F  H   2'-F     H   OH                                                   140 3-F  H   2'-Cl    H   OH                                                   141 3-F  H   3'-F     H   OCH.sub.3                                            142 3-F  H   4'-CN    H   OH                                                   143 3-F  H   4'-Cl    H   OH                                                   144 3-F  H   4'-Cl    H   OCH.sub.3                                            145 3-F  H   4'-Cl    H   CH.sub.3                                             146 3-F  H   3'-Cl    5'-Cl                                                                              OH                                                   147 3-F  H   3'-Cl    4'-Cl                                                                              OH                                                   148 3-F  H   3'-Cl    4'-Cl                                                                              OCH.sub.3                                            149 3-F  4-Cl                                                                               3'-CH.sub.3                                                                             4'-Cl                                                                              OH                                                   150 3-F  H   3'-CH.sub.3                                                                             4'-CH.sub.3                                                                        OH                                                   151 3-F  H   3'-CH.sub.3                                                                             H   OH                                                   152 3-F  H   4'-CH.sub.3                                                                             H   OH                                                   153 3-F  H   4'-CH.sub.3                                                                             H   OCH.sub.3                                            154 3-F  H   H        H   OH                                                   155 3-Cl H   H        H   OH                                                   156 3-Cl H   H        H   H                                                    157 3-Cl H   3'-Cl    H   OH                                                   158 3-Cl H   3'-Cl    5'-Cl                                                                              OH                                                   159 3-Cl H   3'-Cl    4'-Cl                                                                              OH                                                   160 3-Cl H   4-CH.sub.3                                                                              H   OH                                                   161 3-Cl H   4-CF.sub.3                                                                              H   OH                                                   162 3-Cl H   3-CF.sub.3                                                                              H   OCH.sub.3                                            163 3-Cl H   4-Br     H   OH                                                   164 3-Cl H   4-OCH.sub.3                                                                             H   OH                                                   165 4-Cl H   4-SCH.sub. 3                                                                            H   OH     89-90                                         166 4-Cl H   3-CN     H   OH     79-82                                         167 4-Cl H   4-Cl     3-CF.sub.3                                                                         OH     102-104                                       168 4-Cl H   3-Cl     5-Cl                                                                               OH     130-131                                       169 4-Cl H   4-Cl     H   H      oil                                           170 4-Cl H   4-Cl     H   F      oil                                           171 4-Cl H   4-Cl     H   OH     87-88                                         172 4-Cl H   2-F      5-F OH     133-137                                       173 4-Cl H   4-Cl     H   OCH.sub.3                                                                             oil                                           174 4-Cl H   4-Cl     H   OCONHCH.sub.3                                                                         oil                                           175 4-Cl H   4-Cl     H   OCOCH.sub.3                                                                           oil                                           176 4-Cl H   4-OCH.sub.3                                                                             H   OH     88-91                                         177 4-Cl H   4-F      H   OH     90-95                                         178 4-Cl H   4-CH.sub.3                                                                              H   OH                                                   179 4-Cl H   3-CH.sub.3                                                                              H   OH                                                   180 4-Cl H   2-F      H   OCH.sub.3                                                                             120-122                                       181 4-Cl H   4-OCF.sub.3                                                                             H   OH                                                   182 4-Cl H   3-CF.sub.3                                                                              H   OH                                                   183 4-Cl H   4-CF.sub.3                                                                              H   OH                                                   184 4-Cl H   H        H   OH                                                   185 4-Cl H   H        H   OCH.sub.3                                            186 4-Cl H   H        H   OCOCH.sub.3                                          187 4-Cl H   3-CF.sub.3                                                                              H   OH                                                   188 4-Cl H   4-Br     H   OH                                                   189 4-Cl H   3-Cl     4-Cl                                                                               OH                                                   190 4-Cl H   3-Cl     H   OH                                                   191 4-Cl H   3-Cl     H   OCH.sub.3                                            192 4-Cl H   2-Cl     H   OH                                                   193 4-Cl H   3-Cl     5-Cl                                                                               OH     130-131                                       194 4-Cl H   3-Cl     4-CF.sub.3                                                                         OH                                                   195 4-Cl 3-CF.sub.3                                                                         3-Cl     H   OH                                                   196 4-Cl H    .sub.-i-C.sub.3 H.sub.7                                                                H   OH                                                   197 4-Cl H   4-CN     H   OH     126-129                                       198 2-Cl H   2-Cl     H   OH     115-116                                       199 3-Cl H   3-CN     H   OH                                                   200 3-Cl H   4-CN     H   OCH.sub.3                                            201 3-Cl H   4-CHF.sub.2                                                                             H   OH                                                   202 3-Cl H   2-Cl     5-Cl                                                                               CH.sub.3                                             203 3-Cl H   H        H   F                                                    204 3-Cl H   H        H   OH                                                   205 3-Cl 4-CN                                                                               4-Cl     H   OH                                                   206 3-Cl 4-Cl                                                                               3-Cl     4-Cl                                                                               OH                                                   207 3-Cl H   3-Cl     5-Cl                                                                               OH                                                   208 2-CF.sub.3                                                                          H   H        H   OH     72-74                                         209 3-CF.sub.3                                                                          H   4-CF.sub.3                                                                              H   OH                                                   210 3-CF.sub.3                                                                          H   3-CF.sub.3                                                                              H   OH     74.5-77                                       211 4-CF.sub.3                                                                          H   4-CF.sub.3                                                                              H   OH     109-110                                       212 4-CF.sub.3                                                                          H   H        H   OH     85-86                                         213 3-CF.sub.3                                                                          H   H        H   OH     68-70                                         214 H    H   H        H   OH     117-121                                       215 H    H   H        H   OCH.sub.3                                            216 H    H   H        H   OCOCH.sub.3                                          217 H    H   H        H   F                                                    218 H    H   H        H   CH.sub.3                                             219 3-CH.sub.3                                                                          H   H        H   OH                                                   220 3-CH.sub.3                                                                          H   3-CH.sub.3                                                                              H   OH                                                   221 3-CH.sub.3                                                                          H   3-OCH.sub.3                                                                             H   OH                                                   222 3-CH.sub.3                                                                          H   4-SCH.sub.3                                                                             H   OH                                                   223 3-CH.sub.3                                                                          4-CH.sub.3                                                                         4-Cl     H   OCH.sub.3                                            224 3-CH.sub.3                                                                          H   4-Br     H   OH                                                   225 4-CH.sub.3                                                                          H   4-CH.sub.3                                                                              H   OH     oil                                           226 4-CH.sub.3                                                                          H   3-CN     H   OH                                                   227 4-CH.sub.3                                                                          H   4-CN     H   OH                                                   228 4-CH.sub.3                                                                          H   H        H   OH                                                   229 4-CH.sub.3                                                                          H   OCH.sub.2 CH.sub.2 OCH.sub.3                                                            H   H                                                    230 4-CH.sub.3                                                                          H   3-Cl     4-Cl                                                                               H                                                    231 4-CH.sub.3                                                                          H   4-NO.sub.2                                                                              H   OH                                                   232 3-OCH.sub.3                                                                         H   3-CH.sub.3                                                                              4-F OH                                                   233 3-OCH.sub.3                                                                         H   3-Cl     5-Cl                                                                               OH                                                   234 3-OCH.sub.3                                                                         H   H        H   OH                                                   235 3-OCH.sub.3                                                                         4-F 3-Cl     4-Cl                                                                               OH                                                   236 3-OCH.sub.3                                                                         H   3-OCF.sub.3                                                                             H   H                                                    237 3-OCH.sub.3                                                                         H   4-SCF.sub.2 H                                                                           H   OH                                                   238 3-OCH.sub.3                                                                         H   4-CH.sub.2 CH.sub.3                                                                     H   OCOCH.sub.3                                          239 4-OCH.sub.3                                                                         H   3-OCH.sub.3                                                                             H   OH                                                   240 4-OCH.sub.3                                                                         H   3-CN     H   OH                                                   241 4-OCH.sub.3                                                                         H   3-F      4-CN                                                                               OH                                                   242 4-OCH.sub.3                                                                         H   2-CH.sub.3                                                                              H   OH                                                   243 4-OCH.sub.3                                                                         H   4-Br     H   OH                                                   244 4-OCH.sub.3                                                                         H   H        H   H                                                    245 4-OCH.sub.3                                                                         H   3-CF.sub.3                                                                              H   OH                                                   __________________________________________________________________________

                  TABLE 4                                                          ______________________________________                                         General Structure 3                                                            Cmpd.                                                                          No.   R.sup.3 R.sup.4                                                                               R.sub.1.sup.3                                                                        R.sub.1.sup.4                                                                        X       m.p. (°C.)                     ______________________________________                                         246   H       H      H     H     OH      132-133                               247   H       H      H     H     OCH.sub.3                                     248   H       H      H     H     OCOCH.sub.3                                   249   H       H      H     H     F                                             250   1-F     H      H     H     OH      144-145                               251   2-F     H      H     H     OH      118-120                               252   3-F     H      H     H     OH      114-124                               253   2-F     H      8-F   H     OH      146-147                               254   H       H      H     H     H                                             255   H       H      H     H     CH.sub.3                                      256   2-F     H      8-Cl  H     OH                                            257   3-F     H      H     H     OH                                            258   4-F     H      H     H     OH                                            259   2-Cl    H      H     H     OH                                            260   3-Cl    H      8-F   H     OH                                            261   2-CH.sub.3                                                                             H      H     H     OH                                            262   3-CH.sub.3                                                                             H      7-CH.sub.3                                                                           8-CH.sub.3                                                                           OH                                            263   2-CN    H      H     H     OCH.sub.3                                     264   3-CN    H      H     H     OH                                            265   2-CF.sub.3                                                                             H      H     H     OH                                            266   3-CF.sub.3                                                                             H      H     H     OH                                            267   2-F     3-Cl   H     H     OH                                            268   3-F     H      H     H     OH                                            269   2-Cl    H      H     H     OH                                            270   3-Cl    H      H     H     OH                                            271   2-CF.sub.3                                                                             3-F    H     H     OH                                            272   3-CF.sub.3                                                                             H      7-CF.sub.3                                                                           H     OH                                            273   1-F     H      9-F   H     OH                                            ______________________________________                                    

                  TABLE 5                                                          ______________________________________                                         General Structure 4                                                            Cmpd.                                                                          No.   R.sub.1.sup.3                                                                          R.sub.1.sup.4                                                                          R.sup.3                                                                               R.sup.4                                                                              L     m.p. (°C.)                     ______________________________________                                         274   H       H       H      H     CH.sub.2                                    275   H       H       4'-F   H     C═O                                                                              oil                                   276   H       H       4'-F   H     CH.sub.2                                                                             oil                                                                            (diast. A)                            277   H       H       4'-F   H     CH.sub.2                                                                             oil                                                                            (diast. B)                            278   H       H       4'-Cl  H     CH.sub.2                                                                             oil                                   279   H       H       4'-Cl  H     C═O                                                                              oil                                   280   H       H       3'-F   H     CH.sub.2                                                                             oil                                   281   5-F     H       4'-F   H     CH.sub.2                                                                             oil                                   282   H       H       3'-CH.sub.3                                                                           H     CH.sub.2                                    283   H       H       3'-CN  H     CH.sub.2                                    284   H       H       4'-CF.sub.3                                                                           H     CH.sub.2                                    285   H       H       4'-CN  H     CH.sub.2                                    286   H       H       4'-OCH.sub.3                                                                          H     CH.sub.2                                    287   H       H       3'-F   4'-F  CH.sub.2                                    288   4-F     H       4'-F   H     CH.sub.2                                    289   5-Cl    H       3'-F   H     CH.sub.2                                    290   6-Cl    H       3'-Cl  H     CH.sub.2                                    291   6-F     4-Cl    3'-CN  H     CH.sub.2                                    292   5-CH.sub.3                                                                             H       4'-CH.sub.3                                                                           3'-F  CH.sub.2                                    293   6-CH.sub.3                                                                             H       3'-CH.sub.3                                                                           H     CH.sub.2                                    294   4-Cl    H       3'-F   H     CH.sub.2                                    295   H       H       H      H     C═O                                     296   H       H       4'-Cl  H     C═O                                     297   H       H       3'-Cl  4'-Cl C═O                                     298   H       H       4'-CF.sub.3                                                                           H     C═O                                     299   H       H       4'-CN  H     C═O                                     300   5-F     H       3'-CH.sub.3                                                                           H     C═O                                     301   6-F     H       3'-Cl  H     C═O                                     302   H       H       4'-F   3'-F  C═O                                     ______________________________________                                    

                  TABLE 6                                                          ______________________________________                                         General Structure 5                                                            Cmpd.                                                                          No.    R.sub.1.sup.3                                                                            R.sub.1.sup.4                                                                          R.sup.3 R.sup.4                                                                              m.p. (°C.)                       ______________________________________                                         303    H         H       H       H                                             304    H         H       4'-F    H     oil                                     305    H         H       3'-F    H                                             306    H         H       4'-Cl   H                                             307    H         H       3'-Cl   H                                             308    H         H       2'-F    H                                             309    H         H       2'-Cl   H                                             310    H         H       4'-CH.sub.3                                                                            H                                             311    H         H       3'-CH.sub.3                                                                            H                                             312    H         H       3'-CN   H                                             313    H         H       4'-OCH.sub.3                                                                           H                                             314    H         H       3'-CF.sub.3                                                                            H                                             315    H         H       4'-F    3'-F                                          316    H         H       4'-Cl   3'-F                                          317    5-F       H       4'-F    H                                             318    6-F       H       4'-Cl   H                                             319    7-F       H       H       H                                             320    6-Cl      H       H       H                                             321    6-CH.sub.3                                                                               H       3'-F    H                                             322    5-OCH.sub.3                                                                              H       4'-F    H                                             323    6-F       H       H       H                                             324    6-CH.sub.3                                                                               H       H       H                                             325    H         H       4'-CF.sub.3                                                                            H                                             326    H         H       3'-SCH.sub.3                                                                           H                                             327    H         H       4'-CN   H                                             328    6-Cl      7-Cl    3'-F    H                                             329    5-F       7-F     H       H                                             330    6-F       5-F     4'-Cl   H                                             ______________________________________                                    

Formulations

Useful formulations of the compounds of Formulae I, II and III can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 0.1% to 99% by weight of active ingredient(s) and at least one of (a) about 0.1% to 20% surfactant(s) and (b) about 1% to 99.9% solid or liquid inert diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:

                  TABLE 7                                                          ______________________________________                                                     Active  Weight Percent*                                                        Ingredient                                                                             Diluent(s)                                                                               Surfactant(s)                                    ______________________________________                                         Wettable Powders                                                                             20-90      0-74     1-10                                         Oil Suspensions,                                                                              3-50     40-95     0-15                                         Emulsions, Solutions,                                                          (including Emulsifiable                                                        Concentrates)                                                                  Aqueous Suspension                                                                           10-50     40-84     1-20                                         Dusts          1-25     70-99     0-5                                          Granules and Pellets                                                                         0.1-95      5-99.9  0-15                                         High Strength 90-99      0-10     0-2                                          Compositions                                                                   ______________________________________                                          *Active ingredient plus at least one of a Surfactant or a Diluent equals       100 weight percent.                                                      

Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, N.J., but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide," 2nd Ed., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0° C. "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, N.J., as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, microbiological growth, etc.

The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.

For further information regarding the art of formulation, see for example:

H. M. Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41;

R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Mar. 14, 1967, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;

H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4;

G. C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pp. 81-96; and

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.

In the following examples, all parts are by weight unless otherwise indicated.

EXAMPLE 6 Wettable Powder

    ______________________________________                                         α,α-bis(4-chlorophenyl)-2-oxiranemethanol                                                   80%                                                   sodium alkylnaphthalenesulfonate                                                                        2%                                                    sodium ligninsulfonate   2%                                                    synthetic amorphous silica                                                                              3%                                                    kaolinite                13%                                                   ______________________________________                                    

The ingredients are blended, hammer-milled until all the solids are essentially under 50 microns, reblended, and packaged.

EXAMPLE 7 Wettable Powder

    ______________________________________                                         2-[1-(4-chlorophenyl)-2-methylpropyl]oxirane                                                             50%                                                  sodium alkylnaphthalenesulfonate                                                                         2%                                                   low viscosity methyl cellulose                                                                           2%                                                   diatomaceous earth        46%                                                  ______________________________________                                    

The ingredients are blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in diameter. The product is reblended before packaging.

EXAMPLE 8 Granule

    ______________________________________                                         Wettable Powder of Example 6                                                                           5%                                                     attapulgite granules   95%                                                     (U.S.S. 20-40 mesh; 0.84-0.42 mm)                                              ______________________________________                                    

A slurry of wettable powder containing 25% solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged.

EXAMPLE 9 Extruded Pellet

    ______________________________________                                         2-[1-(4-chlorophenyl)-2-methylpropyl]oxirane                                                             25%                                                  anhydrous sodium sulfate  10%                                                  crude calcium ligninsulfonate                                                                             5%                                                  sodium alkylnaphthalenesulfonate                                                                          1%                                                  calcium/magnesium bentonite                                                                              59%                                                  ______________________________________                                    

The ingredients are blended, hammer-milled and then moistened with about 12% water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm openings). the granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged for use and the fines recycled.

EXAMPLE 10 Oil Suspension

    ______________________________________                                         α,α-bis(4-chlorophenyl)-2-oxiranemethanol                                                   25%                                                   polyoxyethylene sorbitol hexaoleate                                                                      5%                                                   highly aliphatic hydrocarbon oil                                                                        70%                                                   ______________________________________                                    

The ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns. The resulting thick suspension may be applied directly, but preferably after being extended with oils or emulsified in water.

EXAMPLE 11 Wettable Powder

    ______________________________________                                         2-[1-(4-chlorophenyl)-2-methylpropyl]oxirane                                                             20%                                                  sodium alkylnaphthalenesulfonate                                                                         4%                                                   sodium ligninsulfonate    4%                                                   low viscosity methyl cellulose                                                                           3%                                                   attapulgite               69%                                                  ______________________________________                                    

The ingredients are thoroughly blended. After grinding in a hammer-mill to produce particles essentially all below 100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged.

EXAMPLE 12 Low Strength Granule

    ______________________________________                                         α,α-bis(4-chlorophenyl)-2-oxiranemethanol                                                   1%                                                    N,N--dimethylformamide   9%                                                    attapulgite granules     90%                                                   (U.S.S. 20-40 sieve)                                                           ______________________________________                                    

The active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the blender is allowed to run for a short period and then the granules are packaged.

EXAMPLE 13 Aqueous Suspension

    ______________________________________                                         2-[[(4,6-dimethoxypyrimidin-2-yl)amino-                                                                   20%                                                 carbonyl]aminosulfonylmethyl]benzoic                                           acid, methyl ester                                                             α,α-bis(4-chlorophenyl)-2-oxiranemethanol                                                     20%                                                 Polyacrylic acid thickener 0.3%                                                dodecylphenol polyethylene glycol ether                                                                   0.5%                                                disodium phosphate         1%                                                  monosodium phosphate       0.5%                                                polyvinyl alcohol          1.0%                                                water                      56.7%                                               ______________________________________                                    

The ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size.

EXAMPLE 14 Low Strength Granule

    ______________________________________                                         2-[1-(4-chlorophenyl)-2-methylpropyl]oxirane                                                              0.1%                                                attapulgite granules       99.9%                                               (U.S.S. 20-40 mesh)                                                            ______________________________________                                    

The active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double-cone blender. After spraying of the solution has been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged.

EXAMPLE 15 Granule

    ______________________________________                                         2-[[(4,6-dimethoxypyrimidin-2-yl)amino-                                                                    50%                                                carbonyl]aminosulfonylmethyl]benzoic                                           acid, methyl ester                                                             α,α-bis(4-chlorophenyl)-2-oxiranemethanol                                                      30%                                                wetting agent               1%                                                 crude ligninsulfonate salt (containing                                                                     10%                                                5-20% of the natural sugars)                                                   attapulgite clay            9%                                                 ______________________________________                                    

The ingredients are blended and milled to pass through a 100 mesh screen. This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The fluidization and spraying are continued until granules of the desired size range are made. The spraying is stopped, but fluidization is continued, optionally with heat, until the water content is reduced to the desired level, generally less than 1%. The material is then discharged, screened to the desired size range, generally 14-100 mesh (1410-149 microns), and packaged for use.

EXAMPLE 16 High Strength Concentrate

    ______________________________________                                         α,α-bis(4-chlorophenyl)-2-oxiranemethanol                                                      99%                                                silica aerogel              0.5%                                               synthetic amorphous silica  0.5%                                               ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produce a material essentially all passing a U.S.S. No. 50 screen (0.3 mm opening). The concentrate may be formulated further if necessary.

EXAMPLE 17 Wettable Powder

    ______________________________________                                         2-[[(4,6-dimethoxypyrimidin-2-yl)amino-                                                                    45%                                                carbonyl]aminosulfonylmethyl]benzoic                                           acid, methyl ester                                                             α,α-bis(4-chlorophenyl)-2-oxiranemethanol                                                      45%                                                dioctyl sodium sulfosuccinate                                                                              0.1%                                               synthetic fine silica       9.9%                                               ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produce particles essentially all below 100 microns. The material is sifted through a U.S.S. No. 50 screen and then packaged.

EXAMPLE 18 Wettable Powder

    ______________________________________                                         2-[1-(4-chlorophenyl)-2-methylpropyl]oxirane                                                             40%                                                  sodium ligninsulfonate    20%                                                  montmorillonite clay      40%                                                  ______________________________________                                    

The ingredients are thoroughly blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in size. The material is reblended and then packaged.

EXAMPLE 19 Oil Suspension

    ______________________________________                                         2-[[(4,6-dimethoxypyrimidin-2-yl)amino-                                                                    26%                                                carbonyl]aminosulfonylmethyl]benzoic                                           acid, methyl ester                                                             α,α-bis(4-chlorophenyl)-2-oxiranemethanol                                                      13%                                                blend of polyalcohol carboxylic                                                                            6%                                                 esters and oil soluble petroleum                                               sulfonates                                                                     xylene                      55%                                                ______________________________________                                    

The ingredients are combined and ground together in a sand mill to produce particles essentially all below 5 microns. The product can be used directly, extended with oils, or emulsified in water.

EXAMPLE 20 Dust

    ______________________________________                                         α,α-bis(4-chlorophenyl)-2-oxiranemethanol                                                   10%                                                   attapulgite              10%                                                   Pyrophyllite             80%                                                   ______________________________________                                    

The active ingredient is blended with attapulgite and then passed through a hammer-mill to produce particles substantially all below 200 microns. The ground concentrate is then blended with powdered pyrophyllite until homogeneous.

EXAMPLE 21 Emulsifiable Concentrate

    ______________________________________                                         2-[1-(4-chlorophenyl)-2-methylpropyl]oxirane                                                               20%                                                chlorobenzene               74%                                                sorbitan monostearate and polyoxyethylene                                                                  6%                                                 condensates thereof                                                            ______________________________________                                    

The ingredients are combined and stirred to produce a solution which can be emulsified in water for application.

Utility

Compounds of this invention are particularly useful for the control of weeds in rice and may be used for both paddy and dryland rice. They may be applied post-emergence to dryland rice, to paddy rice or to rice from which the flood has been removed. The flood may be restored when the chemical has had time to penetrate the weeds. They may also be applied to paddy rice after transplanting as a spray or granule. The application may be made from 3 to 10 days after transplanting.

Rates of 30 to 2000 g/Ha will provide weed control. The compounds are particularly useful for the control of barnyardgrass (Echinochloa crusgalli), a pernicious weed in rice culture, but may also provide complete or partial control of other weeds, particularly gramineous weeds, in rice.

To broaden the spectrum of control, the compounds of this invention may be used in combination with other rice herbicides such as 2-chloro-2',6'-diethyl-N-(butoxymethyl)acetanilide (butachlor), and 2,4-dichlorophenoxyacetic acid (2,4-D).

In addition, compounds of this invention are useful for the control of weeds in cereal crops including wheat and barley. They are effective in both preemergence and postemergence applications. Superior results are obtained as preemergence treatments especially under conditions involving preplant incorporation of the herbicide into the soil.

Rates of 125 to 2000 g/ha will provide weed control. The compounds are particularly useful for the control of wild oats (Avena fatua), green foxtail (Setaria viridis), blackgrass (Alopecurus myosuroides), and annual ryegrass (Lolium multiflorum), but may also provide complete or partial control of other weeds in cereals.

TEST A

Seeds of crabgrass (Digitaria spp.), barnyard-grass (Echinochloa crusgalli), wild oats (Avena fatua), cheatgrass (Bromus secalinus), velvetleaf (Abutilon theophrasti), morningglory (Ipomoea spp.), cocklebur (Xanthium pennsylvanicum), sicklepod (Cassia obtusifolia), sorghum, corn, soybean, sugarbeat, cotton, rice, wheat and purple nutsedge (Cyperus rotundus) were planted and treated preemergence with the test chemicals dissolved in a non-phytotoxic solvent. At the same time, these crops and weed species were treated with a soil/foilage application. At the time of treatment, the plants ranged in height from 2 to 18 cm. Treated plants and controls were maintained in a greenhouse for sixteen days, after which all species were compared to controls and visually rated for response to treatment. The ratings, summarized in Table A, are based on a numerical scale extending from 0=no injury, to 10=complete kill. The accompanying descriptive symbols have the following meanings:

C=chlorosis/necrosis;

B=burn;

D=defoliation;

E=emergence inhibition;

G=growth retardation;

H=formative effect;

U=unusual pigmentation;

X=axillary stimulation;

S=albinism; and

6Y=abscised buds or flowers.

    TABLE A       Cmpd. 171 Cmpd. 20 Cmpd. 21 Cmpd. 22 Cmpd. 32 Cmpd. 2 Cmpd. 174 Cmpd.      26 Cmpd. 1 Cmpd. 24 Cmpd. 51 Cmpd. 120 Cmpd. 208 Cmpd. 213 Cmpd. 212      Rate kg/ha 2.0 2.0 0.4 2.0 2.0 2.0 2.0 0.4 2.0 2.0 2.0 2.0 0.4 2.0 2.0      2.0 2.0        POSTEMERGENCE Morningglory 6B 0 0 0 0 0 0 0 0 0 0 0 0 1B,3G 1B 1B,4H      1B,8G Cocklebur 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3G 1H Nutsedge 0 0 0 0 0 0      0 0 0 0 0 0 4G 9G 4G 8G 0 Crabgrass 0 0 0 2G 6H 0 0 5H 3G 8H 7H 9G 2G 9G      9G 9G 9G Barnyardgrass 1B,9H 0 0 9H 9H 0 0 4H 0 9H 4H 8H 0 9H 9H 9H 9H      Wild Oats 1B,7G 0 0 0 5H 0 0 0 0 0 0 5G 2G 9H 4H 9H 0 Wheat 1B 0 0 0 0 0      0 0 0 0 1H 6G 0 4G 0 7G 0 Corn 2B 0 0 0 0 0 0 0 0 0 1H 0 0 7G 2H 9H 4H      Soybean 2B 0 0 0 0 0 0 0 0 0 0 0 0 2G 0 1B 0 Rice 1B 0 0 0 6G 0 0 0 0 0      2G 8G 2G 9G 9G 9G 9G Sorghum 2B 0 0 0 0 0 0 0 0 0 0 6G 2G 7G 2G 5G 0      Sugar beet 2G 0 0 0 0 0 0 0 0 0 0 0 0 5G 2H 5G 1H Cotton 2G 0 0 0 0 0 0      0 0 0 0 0 0 8G 0 5G 5G Sicklepod 1B 0 0 0 0 0 0 0 0 0 0 Velvetleaf           0 0 0 0 2G 0 Cheat Grass            3G 0 9G 0 7G 0 PREEMERGENCE      Morningglory  6G 2H 0 3H 0 0 0 4G 0 0 3G 0 0 9G 2G 5G 5G Cocklebur -- 0      0 -- 0 0 2G -- 0 0 -- 0 0 0 4G 0 0 Nutsedge 8G 9G 5G 2G 2G 5G 0 9G 10E 0      0 5G 0 10E 5G 10E 0 Crabgrass 4G 10H 9H 10H 10H 9H 0 9G 10E 2G 10H 10H      9H 10E 8H 10H 9H Barnyardgrass 9H 10H 9H 10H 10E 6H 0 9G 10H 2G 9H 10H      9H 10H 9H 9H 9H Wild Oats 9H 10H 9H 7G 10H 7H 0 7G 9H 0 10H 10H 8G 10H      7G 9H 4G Wheat 8H 10H 9H 10H 6G 9H 0 3G 10H 0 10H 9H 8G 5G 8G 9H 6G Corn      7H 9H 0 9H 9H 3H 4G 0 9H 5G 2H 6H 0 9H 8H 9H 9H Soybean 4G 0 0 0 3G 0 3G      0 4G 0 0 0 0 6G 2H 8G 2G Rice 10E 10E 10E 10E 10E 9H 4G 3G 10E 0 10E 10E      8H 10E 9H 10E 9H Sorghum 9H 10E 9H 10H 10H 6H 7H 6G 9H 6H 10H 10H 5G 9H      9H 10H 9H Sugar beet 7G 3H 0 0 2G 0 4G 0 2G 0 0 0 0 10C 5G 5C,9G 2H      Cotton 3G 0 0 0 0 0 0 0 0 0 0 0 0 6G 4G 7G 0 Sicklepod 2G 2G 0 0 0 0 9G      0 2G 0 0 Velvetleaf            0 0 8G 2G 5G 4G Cheat Grass            7G      4G 10E 5G 9H 4G         Cmpd. 214 Cmpd. 121 Cmpd. 175 Cmpd. 173 Cmpd. 169 Cmpd. 117 Cmpd. 168 C      mpd. 275 Cmpd. 281 Cmpd. 276 Cmpd. 278 Cmpd. 251 Cmpd. 253 Cmpd. 193      Rate kg/ha 2.0 2.0 2.0 2.0 0.4 0.4 2.0 2.0 0.4 2.0 0.4 0.4 0.4 2.0        POSTEMERGENCE Morningglory 1B,4G 1B 1B,2H 0 7B 0 4B 2B 0 2G 1B 0 0 4B      Cocklebur 2G 0 0 0 0 0 0 0 0 0 0 0 0 0 Nutsedge 5C,9G 6G 0 0 0 0 0 0 0 0      0 0 0 0 Crabgrass 9G 9G 6G 2C,9G 0 8G 1B,8G 2B,9G 8G 9H 8G 8H 8H 1B,8G      Barnyardgrass 9H 9H 7H 9H 9H 9H 3B,9H 7B,9H 9H 9H 7H 5H 8H 3B,9H Wild      Oats 5H 9H 2H 7H 0 0 1B 1B 0 8H 7G 0 0 1B Wheat 8G 3G 0 0 0 0 2B 0 0 6G      0 0 0 2B Corn 9H 9H 2G 1H 0 0 2B 0 0 6H 0 0 0 2B Soybean 2H 1H 0 1B 0 0      3B 1B 8G 4H 3H 0 0 3B Rice 9G 9G 0 0 0 2G 2B 4G 3G 9G 0 0 4G 2B Sorghum      8H 4G 0 2C,9H 0 0 1B 0 2G 6G 8H 0 0 1B Sugar beet 4H 3H 0 0 0 0 1B,4G 4H      0 4H 2H 0 0 1B,4G Cotton 6G 5G 0 0 0 0 4B,8G 0 0 1H 0 0 0 4B,8G Sicklepod           -- -- -- -- -- -- -- Velvetleaf 1C 0 0 4G        0 0 1B Cheat Grass      9G 3G 0 0        0 0 1B PREEMERGENCE Morningglory 9G 8G 0 0 0 3G 0 9G 0      9G 5G 0 0 0 Cocklebur 0 0 0 0 0 0 0 7G 0 2G 2G 0 0 0 Nutsedge 4G 5G 0 0      0 5G 0 0 0 2H 0 0 0 0 Crabgrass 9H 10H 2H 9H 5G 9H 10H 10H 10E 10E 6G 8H      4G 10H Barnyardgrass 10H 10H 9H 9H 10E 9H 10H 10H 10H 10E 10E 9H 9H 10H      Wild Oats 8G 10H 9G 9H 0 9H 7G 7G 7H 8G 0 7G 5G 7G Wheat 8G 8G 5G 9H 0      3G 6G 5G 5H 10E 5G 6G 3G 6G Corn 9H 9H 2G 7H 0 2G 2G 2G 0 5G 0 2G 3G 2G      Soybean 7G 7G 0 0 0 0 0 0 0 10E 0 0 0 0 Rice 10E 10E 6G 9H 2G 7G 7G 2G      10H 10E 4G 4G 4G 7G Sorghum 9H 10H 8G 9H 4G 4G 6G 8H 10H 10E 10H 0 0 6G      Sugar beet 8G 10C 5G 2G 0 0 5G 7G 3H 10C 0 7G 0 5G Cotton 5G 8G 0 0 0 3G      0 8G 0 8G 4G 0 0 0 Sicklepod     -- -- -- -- -- -- -- Velvetleaf 5H 5G 0      0        0 0 0 Cheat Grass 10H 10H 4G 5G        0 0 3G

TEST B

Sixteen-cm diameter Wagner pots, equipped with a stoppered drain opening near the bottom of the side wall, were filled with Woodstown sandy loam. About 1500 ml of water were added to each pot to bring the water level to a point 3 cm above the soil surface. Japonica and Indica rice seedlings were transplanted. Also, a number of barnyardgrass (Echinochloa crusgalli) seeds were added to each pot. At the same time, seedlings or tubers of the following species were transplanted into the muddy soil: water plaintain (Alisma trivale), Scirpus (Scirpus mucranatus), and Cyperus (Cyperus difformis). The weed species selected for this test are of economic importance in major rice-growing areas. The chemical treatments were applied within hours after transplanting two additional species: water chestnut (Eleocharis spp.) and arrowhead (Sagittaria latifolia). Shortly after treatment, the drain hold was opened to drop the water level by two cm. Water was then added to restore the water level to its original height. The following day the draining and refilling process was repeated. The pots were then maintained in the greenhouse. Rates of application and plant response ratings made 21 days after treatment are summarized in Table B. Note that Compound 171 alone effectively controls barnyardgrass and the combination of Compound 1 and 2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoic acid, methyl ester controls a broad spectrum of rice weeds.

                  TABLE B                                                          ______________________________________                                         Combination Test                                                               Rate     % Injury or Control                                                   g/ha     R.sub.J                                                                              R.sub.I                                                                               BYG  WC    A    SC   CY    WP                            ______________________________________                                         With Treatment:                                                                 ##STR23##                                                                      50       0     0      50   87   75   80   83    93                            100      20     0      80   95   70   93   97    95                            200      33    20      97  100   85   100  100  100                            400      40    20     100  100   95   100  100   97                            With Treatment 171:                                                             50       0     0      50  0     0    0    0    0                               75       0     0      85  0     0    0    0    0                              100       0     0      95  0     0    0    0    0                              With Treatment 171 and:                                                         ##STR24##                                                                      50 + 50  0     0      95   95   60   95   97   100                             50 + 75  0     0      95   95   68   90   80    85                             50 + 100                                                                                0    10     100   97   75   85   90    85                            100 + 50 10     7      95  100   90   85   90   100                            100 + 75  0     0      97  100   85   90   95   100                            100 + 100                                                                               20    20      97  100   85   93   93   100                            200 + 50 20    20     100  100   85   87   97    95                            200 + 75 20    20      97  100   85   93   100  100                            200 + 100                                                                               20    20     100  100   97   100  95    95                            400 + 50 30     0     100  100   100  100  100  100                            400 + 75 25    20     100  100   100  100  100  100                            400 + 100                                                                               23    20     100  100   100  100  100  100                            ______________________________________                                          R.sub.J = Japonica Rice                                                        R.sub.I = Indica Rice                                                          BYG = Barnyardgrass                                                            WC = Waterchestnut                                                             A = Arrowhead                                                                  SC = Scirpus                                                                   CY = Cyperus                                                                   WP = Water Plaintain                                                     

TEST C

Barnyardgrass seed was sown into 12 cm diameter wax cups containing Sassafras sandy loam soil, which was kept moist but not flooded until seedlings began to emerge. At that time, rice (Japonica and Indica varieties) was transplanted into similar cups when the rice was at the 2-3 leaf stage. A permanent flood was established 4 or 5 days following transplanting the rice. Both the rice and barnyardgrass were flooded 3.0 cm deep.

Following the flood, compounds were applied directly to the paddy after being formulated in a nonphytotoxic solvent.

Rice growth and barnyardgrass control were evaluated approximately 17 days following compound application. Rice injury was evaluated by analysis of seedling fresh weight and converted to % injury relative to untreated plants. Barnyardgrass control was visually determined using a scale of 0 to 100% (0=no control; 100=complete control). Each treatment was replicated twice. The results are summarized in Table C.

                  TABLE C                                                          ______________________________________                                         Barnyardgrass Control and Rice Tolerance                                                    % Control or Injury                                               Compound Rate                  Rice                                            Number   (g/ha)    Barnyardgrass                                                                              (Japonica/Indica)                               ______________________________________                                         171      0.25      0           0/0                                                      1         0           0/0                                                      4         0           0/0                                                      16        23          0/0                                                      63        63          0/0                                                      250       93          0/0                                                      1000      100         0/0                                              21      0.25      0           10/20                                                    1         0           0/0                                                      4         0           0/0                                                      16        0           0/0                                                      63        40          10/10                                                    250       95           0/20                                                    1000      100         20/0                                             1       0.25      0           0/0                                                      1         0           0/0                                                      4         0           0/0                                                      16        0           0/0                                                      63        17          0/0                                                      250       65          0/0                                                      1000      97           0/55                                           166      0.25      0           0/0                                                      1         0           0/0                                                      4         0           0/0                                                      16        0           0/0                                                      64        72          0/0                                                      250       100         0/0                                                      1000      100         20/0                                            104      0.25      0           0/0                                                      1         0           0/0                                                      4         0           0/0                                                      16        0           0/0                                                      64        33          0/0                                                      250       100         0/0                                                      1000      100         0/0                                             106      0.25      0           0/0                                                      1         0           0/0                                                      4         0           0/0                                                      16        0           0/0                                                      64        50          0/0                                                      250       100         0/0                                                      1000      100         0/0                                             275      0.25      0           0/0                                                      1         0           0/0                                                      4         0           0/0                                                      16        0           0/0                                                      64        25          20/0                                                     250       100         0/0                                                      1000      100         0/0                                             276      0.25      --          25/0                                                     1         --          20/0                                                     4         --          0/0                                                      16        --           0/40                                                    30        74          --                                                       64        98          0/0                                                      125       99          --                                                       250       100          0/25                                                    1000      100         35/70                                           ______________________________________                                    

TEST D

Pre-germinated Indica rice (Oryza sativa) seeds are sown into Wagner pots containing wet Sassafras sandy loam soil. Seeds of barnyardgrass (Echinochloa crusgalli) and hemp sesbania (Sesbania exaltata) are sown into additional Wagner pots. Compounds, formulated in a non-phytotoxic solvent, are applied directly to the Wagner pots either prior to establishing a permanent flood or shortly thereafter. Application of compounds is normally 3 to 12 days after seeding. Evaluation is conducted 21 to 25 days after treatment. Ratings are in % weed control or rice injury, visually assessed, relative to untreated controls. The results are summarized in Table D.

                  TABLE D                                                          ______________________________________                                                Rate  Preemergence  Postemergence                                       Treatment                                                                               g/ha    R      BYG   SES  R    BYG  SES                               ______________________________________                                         171       63      60     0    0     0    0   0                                          125      87    40    0     0   33   0                                          250     100    75    0    42   60   0                                          500     100    97    0    70   80   0                                 ______________________________________                                          R = Indica Rice                                                                BYG = Barnyardgrass                                                            SES = Hemp Sesbania                                                      

TEST E

Seeds of rice (Oryza sativa), barnyardgrass (Echinochloa crusgalli), morningglory (Ipomoea purpurea), wild oats (Avena fatua), nutsedge (Cyperus esculentus) and crabgrass (Digitaria ischaemum) are sown into 25 cm diameter plastic pots containing Sassafras sandy loam soil. Compounds, formulated in a non-phytotoxic solvent, are applied as preemergence and postemergence (rice=2 to 3 leaves) treatments. Evaluation, by visual assessment, is conducted 21 to 25 days following treatment. Weed control and rice injury ratings are based on a % system relative to the untreated controls. The results are summarized in Table E.

                  TABLE E                                                          ______________________________________                                         Treatment                                                                              Rate g/ha R      BYG  NS   MG    WO   C                                ______________________________________                                         171 (post)                                                                             125       0       0   0    0     0     0                                       250       0       0   0    0     0     0                                       500       0      70   0    0     0    40                                       1000      0      80   0    0     0    50                               171 (pre)                                                                              125       0       0   0    0     0     0                                       250       0      90   0    0     0     0                                       500       0      95   0    0     0    65                                       1000      0      95   0    0     0    85                               ______________________________________                                          R = Rice                                                                       BYG = Barnyardgrass                                                            NS = Nutsedge                                                                  MG = Morningglory                                                              WO = Wild Oats                                                                 C = Crabgrass                                                            

TEST F Postemergence

Two round pans (25 cm diameter by 12.5 cm deep) were filled with Sassafras sandy loam soil. One pan was planted with blackgrass (Alopecurus myosuroides), sugar beets, nutsedge (Cyperus rotundus) tubers, rape (Brassica napus), crabgrass (Digitaria sanguinalis), sicklepod (Cassia obtusifolia), teaweed (Sida spinosa), jimsonweed (Datura stramonium), velvetleaf (Abutilon theophrasti), and giant foxtail (Setaria faberii). The other pan was planted with wheat, cotton, rice, corn, soybean, wild oats (Avena fatua), cocklebur (Xanthium pensylvanicum), morningglory (Ipomoea hederacea), johnsongrass (Sorghum halepense) and barnyardgrass (Echinochloa crusgalli). The plants were grown for approximately fourteen days, then sprayed post-emergence with the chemicals dissolved in a non-phytotoxic solvent.

Preemergence

Two round pans (25 cm diameter by 12.5 cm deep) were filled with Sassafras sandy loam soil. One pan was planted with weed, jimsonweed, velvetleaf, and giant foxtail. The other pan was planted with wheat, cotton, rice, corn, soybeans, wild oats, cocklebur, morningglory, johnsongrass, and barnyardgrass. The two pans were sprayed preemergence with the chemicals dissolved in a non-phytotoxic solvent.

Treated plants and controls were maintained in the greenhouse for 28 days, then all treated plants were compared to controls and visually rated for plant response.

Response ratings are based on a scale of 0 to 100 where 0=no effect and 100=complete control. Some compounds were rated using a scale where 0=no injury and 10=complete control; G=growth retardation. A dash (-) response means no test.

Response ratings are contained in Table F.

    TABLE F       Cmpd. 20 Cmpd. 21 Cmpd. 22 Cmpd. 26 Cmpd. 24 Cmpd. 51 Cmpd. 118 Cmpd.      114 Cmpd. 78 Cmpd. 115 POSTEMERGENCE Rate g/ha 1000 250 1000 4000 1000      1000 1000 1000 250 1000 250 1000 250 1000 250 62 1000 250 62 1000      250      Corn 0 0 2G 2G 0 0 0 0 0 0 0 0 0 0 0 0 80 60 40 0 0 Wheat 0 0 0      0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Rice 0 0 0 5G 0 0 0 0 0 20 0 0 0 50      0 0 30 0 0 20 0 Soybean 0 0 0 0 0 0 0 0 0 0 0 40 0 0 0 0 30 0 0 0 0      Cotton 0 0 0 2G 0 0 0 0 0 0 0 0 0 0 0 0 30 0 0 0 0 Sugar beet 0 0 0 0 0      0 20 0 0 40 30 0 0 0 0 0 0 0 0 0 0 Rape -- -- -- -- -- -- 20 0 0 20 0 0      0 0 0 0 0 0 0 0 0 Crabgrass 0 0 3G 8G 7G 0 0 0 0 90 30 80 70 100 90 20      90 50 30 100 80 Johnsongrass 0 0 2G 7G 5G 0 0 70 20 0 0 40 0 70 20 0 60      30 0 0 0 Blackgrass 0 0 0 5G 0 0 0 0 0 90 0 80 70 50 0 0 40 0 0 100 30      Barnyardgrass 0 0 5G 9G 3G 0 0 0 0 90 30 30 0 100 0 0 70 30 0 90 60      Nutsedge 0 0 0 5G 0 0 0 20 0 0 0 30 0 0 0 0 0 0 0 0 0 Giant Foxtail 0 0      7G 6G 4G 0 0 30 0 30 0 0 0 60 50 0 70 40 0 90  20 Wild Oats 0 0 0 7G 0      -- 0 0 0 80 0 60 30 0 0 0 0 0 0 0 0 Cocklebur 2G 0 0 0 0 0 0 50 0 20 0      30 0 0 0 0 0 0 0 0 0 Morningglory 0 0 0 0 0 0 0 40 20 20 0 30 0 0 30 0 0      0 0 20 0 Teaweed 0 0 0 2G 0 0 0 20 0 0 20 80 70 20 0 0 50 30 0 30 0      Sicklepod 0 0 0 3G 0 0 0 0 0 -- 20 0 0 20 0 0 0 0 0 30 0 Jimsonweed 0 0      0 0 0 0 0 30 0 20 20 0 0 60 30 0 30 0 0 60 0 Velvetleaf 0 0 0 0 0 2G 0 0      0 0 0 0 0 60 0 0 0 0 0 30 0 PREEMERGENCE Rate g/ha 1000 250 1000 250 62      1000 250 1000 250 4000 1000 250 1000  250  1000 250 62 1000 250                Corn 0 0 0 0 0 0 0 0 0 0 0 0 30 0 0 0 0 60 0 0 0 0 0 0 0 0 0      Wheat 0 0 0 0 0 0 0 0 0 100 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 20 0 Rice 0 0      6G 2G 0 3G 0 6G 2G 100 0 0 100 40 40 0 0 90 50 60 20 0 70 40 0 100 50      Soybean 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 30 0 0 0 0 Cotton 0      0 0 0 0 0 0 2G 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Sugar beet 0 0 0 0      0 0 0 2G 0 0 0 0 0 0 90 70 30 0 0 30 0 0 70 40 0 80  30 Rape -- -- -- --      -- -- -- -- -- 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Crabgrass 4G 0 7G 0 0      9G 2G 2G 0 100 40 0 100 40 100 100 70 100 100 100 90 20 100 90 60 100      100 Johnsongrass 0 0 0 0 0 8G 2G 0 0 100 70 0 100 40 90 60 30 100 70 100      20 0 100 80 30 60 20 Blackgrass 2G 0 3G 0 0 6G 2G 7G 2G 100 0 0 20 0 40      0 0 90 60 70 50 0 100 90 60 90 30 Barnyardgrass 0 0 7G 0 0 7G 2G 2G 0      100 0 0 100 30 90 80 40 100 90 100 90 20 100 100 50 100 50 Nutsedge 0 0      0 0 0 0 0 3G 0 0 0 0 0 0 40 0 0 50 0 0 0 0 0 0 0 0 0 Giant Foxtail 0 0      -- 0 0 -- -- -- -- 100 80 0 30 0 90 70 40 100 80 100 100 90 100 100 70      100 40 Wild Oats 0 0 0 0 0 0 0 0 0 100 30 0 0 0 0 0 0 90 40 20 0 0 80 30      0 60 0 Cocklebur 3G 0 -- 0 0 0 0 5G 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0      0 Morningglory 0 0 0 0 0 0 0 0 0 0 0 0 0 0 50 30 30 0 0 0 0 0 30 0 0 0 0      Teaweed 2G 0 0 0 0 0 0 6G 2G 80 70 0 0 0 70 50 0 30 0 20 20 0 50 30 0 0      0 Sicklepod 0 0 0 0 0 0 0 0 0 0 0 0 0 0 50 30 0 30 0 40 0 0 50 30 0 0 0      Jimsonweed 4G 0 0 0 0 2G 0 0 0 50 0 0 0 0 50 0 0 0 0 30 20 20 30 0 0 20      0 Velvetleaf 3G 0 0 0 0 2G 0 3G 0 0 0 0 0 0 70 30 0 0 0 20 0 0 0 0 0 0      0   Cmpd. 115 Cmpd. 276 Cmpd. 280 Cmpd. 278 Cmpd. 246 POSTEMERGENCE Rate      g/ha 62 1000 250 62 1000 250 1000 250 1000 250 1000 250 62        Corn 0 0 0 0 50 30 0 0 0 0 0 0 0 Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 Rice      0 60 0 0 0 0 0 0 0 0 0 0 0 Soybean 0 0 0 0 50 30 40 0 30 0 0 0 0 Cotton      0 0 0 0 0 0 30 0 30 0 0 0 0 Sugar beet 0 0 0 0 0 0 0 0 0 0 40 0 0 Rape 0      20 0 0 0 0 0 0 0 0 30 0 0 Crabgrass 20 90 90 20 90 70 80 50 80 50 80 40      30 Johnsongrass 0 0 0 0 40 0 40 0 50 0 60 0 0 Blackgrass 0 80 20 0 40 0      30 0 30 0 0 0 0 Barnyardgrass 0 90 0 0 50 0 30 0 30 0 60 0 0 Nutsedge 0      20 0 0 80 70 0 0 0 0 30 0 0 Giant Foxtail 0 60 0 0 40 0 0 0 40 0 40 0 0      Wild Oats 0 20 0 0 0 0 0 0 30 0 0 0 0 Cocklebur 0 0 0 0 0 0 30 0 50 30      50 30 0 Morningglory 0 20 0 0 30 0 50 30 30 0 60 30 0 Teaweed 0 40 20 0      30 0 30 0 30 0 50 30 0 Sicklepod 0 20 0 0 0 0 50 30 0 0 -- -- --      Jimsonweed 0 50 20 0 50 30 50 0 50 30 30 0 0 Velvetleaf 0 20 0 0 0 0 0 0      0 0 30 0 0 PREEMERGENCE Rate g/ha     1000 250 62 1000 250 62 1000 250      62 1000 250 62         Corn 0 0 0 0 30 0 0 0 0 0 0 0 0 60 30 0 Wheat 0 0 0 0 0 0 0 0 0 0 0 0      0 0 0 0 Rice 0 80 80 20 90 30 0 30 0 0 0 0 0 80 0 0 Soybean 0 20 0 0 0 0      0 0 0 0 0 0 0 0 0 0 Cotton 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Sugar beet 0      20 0 0 90 50 30 30 0 0 30 0 0 90 50 0 Rape 0 0 0 0 40 0 0 0 0 0 50 0 0 0      0 0 Crabgrass 60 100 60 0 100 90 70 100 100 60 100 70 50 100 90 70      Johnsongrass 0 50 0 0 100 90 50 100 90 40 100 60 30 60 0 0 Blackgrass 0      70 30 0 90 50 0 50 30 0 70 30 0 70 0 0 Barnyardgrass 0 100 90 20 100 100      50 100 100 90 100 70 30 80 0 0 Nutsedge 0 0 0 0 100 90 70 0 0 0 0 0 0 80      70 50 Giant Foxtail 0 100 100 60 100 100 60 100 90 60 100 90 60 80 40 0      Wild Oats 0 30 0 0 50 0 0 0 0 0 70 30 0 30 0 0 Cocklebur 0 0 0 0 70 50      30 0 0 0 0 0 0 50 30 0 Morningglory 0 0 0 0 50 0 0 0 0 0 0 0 0 50 30 0      Teaweed 0 0 0 0 50 30 0 0 0 0 40 0 0 50 30 0 Sicklepod 0 0 0 0 50 30 0      40 0 0 0 0 0 -- -- -- Jimsonweed 0 0 0 0 50 30 0 30 0 0 50 30 0 50 30 0      Velvetleaf 0 0 0 0 50 30 0 0 0 0 50 30 0 50 30 0

TEST G

Sixteen Wagner pots were filled with Anakida clay loam. About 1500 ml of water was added to each pot to bring the water level to a point 1 cm above the soil surface. Japonica rice (cultivar "Nihonbare") seedlings at the 2.2-2.5 leaf-stage were transplanted. At the same time, plastic pots (11.4 cm diameter) were filled with Anakida clay loam, watered to 1 cm above the soil and a number of barnyardgrass (Echinochloa oryzicola) seeds were sowed.

The chemical treatments were applied to rice three to four days after transplanting, and at the 0.5 leaf-stage and the 1.5 leaf-stage to barnyardgrass after adding water to bring the water level to a point 3 cm above the soil surface. The water level in all test pots was maintained thereafter at the same level by adding water when necessary. The pots were maintained in a greenhouse. Tested chemical, rates of application, and plant response ratings made 14 days or 21 days after treatment are summarized in Table G. The ratings are based on a numerical scale extending from 0=no injury, to 10=complete kill.

                  TABLE G                                                          ______________________________________                                         Barnyardgrass Control and Rice Tolerance                                                     Barnyardgrass                                                            Rate  Control                                                          Compound  (g/ha)  0.5 LS     1.5 LS                                                                               Rice Injury                                 ______________________________________                                          78        32      0         0     1.5                                                    64      7         0     1                                                     125     10         3     1                                                     250     10         5     2                                           168       125      5         0     1.5                                                   250     10         0     1                                                     500     10         3     0                                                     1000    10         5     0.5                                         106       125      0         0     0                                                     250      9         3     0.5                                                   500     10         8     0                                                     1000    10         10    0.5                                         193       125      5         0     1.5                                                   250     10         0     1                                                     500     10         3     0                                                     1000    10         5     0.5                                         ______________________________________                                    

TEST H

Two evaluations were conducted. In the first evaluation, plastic trays were lined with polyethylene liners are filled with pasteurized Sassafras sandy loam soil (pH 6.5, 1% O.M.). One tray was planted with wheat (Triticum aestivum), barley (Hordeum vulgare), wild oats (Avena fatua), cheatgrass (Bromus secalinus), blackgrass (Alopecurus myosuroides), annual bluegrass (Poa annua), green foxtail (Setaria viridis), annual ryegrass (Lolium multiflorum), and rapeseed (Brassica napus). A second tray was planted with Matricaria inodora, cleavers bedstraw (Galium aparine), Russian thistle (Salsola kali), shepherdspurse (Capsella bursapastoris), kochia (Kochia scoparia), black nightshade (Solanum nigrum), speedwell (Veronica persica), wild buckwheat (Polygonum convolvulus) and sugarbeet (Beta vulgaris). For postemergence treatments, the first tray was planted 14 days before spraying, and the second tray was planted 22 days before treatment. Plants in the postemergence treatments ranged in height from 1 to 15 cm, depending on species. Wheat, barley and wild oats were in the 2-leaf stage of development (Zadoks stage 11). A second set of trays were prepared in an identical manner before spraying to serve as preemergence treatments. The herbicide was diluted in a nonphytotoxic solvent and applied to the trays using a belt sprayer. Plants were grown in a greenhouse for 21 days at which time visual ratings were made by comparing to an untreated control treatment. Ratings were based on a scale of 0=no effect to 100=complete kill. The results are summarized in Table H.

The second evaluation consisted of two 25 cm pans filled with either Sassafras sandy loam soil or Tama silt loam soil (pH 5.5, 3% O.M.). The first pot was prepared and seeded before herbicide treatment with wheat, barley, wild oats, cheatgrass, blackgrass, annual bluegrass, green foxtail, annual ryegrass, rapeseed and sugarbeet. The second pot was covered with a polyethylene bag and the soil used to cover the seed was added. This soil was then treated with the herbicide and thoroughly mixed. The seeds were then placed in the pot and covered with the treated soil. Plants were grown and evaluated in the manner previously described. The results are summarized in Tables I and J.

                  TABLE H                                                          ______________________________________                                         Plant Response Ratings for the Wheat and Barley                                Herbicide Screen                                                                         Compound 120                                                                   Rate (g/ha)                                                          Test Plant  2000     1000    500   250   125                                   ______________________________________                                         Preemergence                                                                   Wheat       40       0       0     0     0                                     Barley      50       0       0     0     0                                     Sugarbeets  80       80      80    50    0                                     Rapeseed    30       10      0     0     0                                     Wild Oats   80       60      40    20    0                                     Cheatgrass  30       20      20    0     0                                     Blackgrass  60       30      30    0     0                                     Annual Bluegrass                                                                           70       30      30    10    0                                     Green Foxtail                                                                              100      90      80    30    20                                    Italian Ryegrass                                                                           100      90      60    20    0                                     Matricaria inodora                                                                         20       10      0     0     0                                     Galium aparine                                                                             30       0       0     0     0                                     Russian Thistle                                                                            30       20      0     0     0                                     Shepherdspurse                                                                             40       0       0     0     0                                     Kochia      60       50      50    0     0                                     Black Nightshade                                                                           30       0       0     0     0                                     Speedwell   60       0       0     0     0                                     Wild Buckwheat                                                                             0        0       0     0     0                                     Postemergence                                                                  Wheat       20       0       0     0     0                                     Barley      60       50      20    20    0                                     Sugarbeets  30       0       0     0     0                                     Rapeseed    0        0       0     0     0                                     Wild Oats   60       50      20    20    0                                     Cheatgrass  30       0       0     0     0                                     Blackgrass  80       80      60    60    40                                    Annual Bluegrass                                                                           30       20      0     0     0                                     Green Foxtail                                                                              70       50      50    50    20                                    Italian Ryegrass                                                                           60       40      40    0     0                                     Matricaria inodora                                                                         0        0       0     0     0                                     Galium aparine                                                                             60       20      0     0     0                                     Russian Thistle                                                                            0        0       0     0     0                                     Shepherdspurse                                                                             0        0       0     0     0                                     Kochia      40       10      10    0     0                                     Black Nightshade                                                                           20       0       0     0     0                                     SpeedWell   40       40      40    10    0                                     Wild Buckwheat                                                                             0        0       0     0     0                                     ______________________________________                                    

                  TABLE 1                                                          ______________________________________                                         Plant Response Ratings for the Application                                     Preemergence and Preplant Incorporated in                                      Sassafras Sandy Loam Soil                                                             Compound 120                                                                                 Preplant                                                         Preemergence  Incorporated                                                     Rate (g/ha)                                                             Species  2000   1000   500  250  2000 1000 500  250                            ______________________________________                                         Wheat    10     0      0    0    35   10   0    0                              Barley   10     0      0    0    60   50   40   0                              Sugarbeet                                                                               75     60     40   0    85   70   65   30                             Rapeseed 30     20     0    0    60   40   20   0                              Wild Oats                                                                               98     60     40   10   100  100  98   75                             Cheatgrass                                                                              20     0      0    0    98   90   85   20                             Blackgrass                                                                              95     80     80   80   98   90   70   50                             Annual   50     10     0    0    95   85   80   20                             Bluegrass                                                                      Green    95     90     90   70   98   95   75   65                             Foxtail                                                                        Annual   95     70     20   0    100  100  98   80                             Ryegrass                                                                       ______________________________________                                    

                  TABLE J                                                          ______________________________________                                         Plant Response Ratings for the Application                                     Preemergence and Preplant Incorporated in                                      Tama Silt Loam Soil                                                                   Compound 120                                                                                 Preplant                                                         Preemergence  Incorporated                                                     Rate (g/ha)                                                             Species  2000   1000   500  250  2000 1000 500  250                            ______________________________________                                         Wheat    0      0      0    0    20   20   0    0                              Barley   0      0      0    0    60   20   0    0                              Sugarbeet                                                                               50     0      0    0    60   60   30   0                              Rapeseed 30     0      0    0    60   35   10   0                              Wild Oats                                                                               30     0      0    0    100  95   95   40                             Cheatgrass                                                                              20     0      0    0    90   90   50   20                             Blackgrass                                                                              100    90     90   80   95   90   50   50                             Annual   40     20     0    0    100  95   40   0                              Bluegrass                                                                      Green    95     95     80   30   100  90   90   60                             Foxtail                                                                        Annual   75     20     0    0    100  100  90   20                             Ryegrass                                                                       ______________________________________                                     

What is claimed is:
 1. Compounds of the formula ##STR25## wherein R¹ is ##STR26## R² is C₂ -C₄ alkyl, C₃ -C₆ cycloalkyl, or ##STR27## where R³, R⁴, R₁ ³ and R₁ ⁴ are independently H, F, Cl, Br, CF₃, CN, NO₂, OCH₂ CH₂ OCH₃, C₁ -C₃ alkyl, C₁ -C₃ haloalkyl, C₁ -C₃ alkoxy, C₁ -C₃ haloalkoxy, C₁ -C₃ alkylthio, or C₁ -C₃ haloalkylthio; andX is F, CH₃, or OR⁶ ;where R⁶ is H, C₁ -C₃ alkyl, C(O)CH₃ or C(O)NHCH₃.
 2. The compounds of claim 1 whereinX is OR⁶.
 3. The compounds of claim 1 whereR³, R⁴, R₁ ³ and R₁ ⁴ are independently H, F, Cl, Br, CF₃, OCH₂ CH₂ OCH₃, C₁ -C₃ alkyl, C₁ -C₃ haloalkyl, C₁ -C₃ alkoxy, or C₁ -C₃ alkylthio; X is OR⁶ ; and R⁶ is H, C₁ -C₃ alkyl or C(O)CH₃.
 4. The compounds of claim 1 where R₂ is ##STR28## R₃, R₄, R₁ ³ and R₁ ⁴ are independently H, F, Cl, Br, CF₃, CN, OCH₂ CH₂ OCH₃, C₁ -C₃ alkyl, C₁ -C₃ haloalkyl, C₁ -C₃ alkoxy, C₁ -C₃ haloalkoxy, C₁ -C₃ alkylthio, or C₁ -C₃ haloalkylthio each substituted at the 3, 4 or 5 position.
 5. The compounds of claim 4 where R³, R⁴, R₁ ³ and R₁ ⁴ are independently H, F, Cl, CF₃, C₁ -C₃ alkoxy, or C₁ -C₃ alkyl and X is OH or OCH₃.
 6. The compound of claim 5 which is α,α-bis(4-chlorophenyl)-2-oxiranemethanol.
 7. The compound of claim 5 which is α-phenyl-α-oxiranemethanol.
 8. The compound of claim 5 which is α,α-bis(4-fluorophenyl)-2-oxiranemethanol.
 9. The compound of claim 5 which is α-(4-chlorophenyl)-α-phenyloxiranemethanol.
 10. The compound of claim 5 which is α-(4-chlorophenyl)-α-(3,5-dichlorophenyl)oxiranemethanol.
 11. An agriculturally suitable composition for controlling the growth of undesired vegetation comprising an effective amount of the compound of claim 1 and at least one of the following: surfactant, solid or liquid diluent.
 12. An agriculturally suitable composition for controlling the growth of undesired vegetation comprising an effective amount of the compound of claim 2 and at least one of the following: surfactant, solid or liquid diluent.
 13. An agriculturally suitable composition for controlling the growth of undesired vegetation comprising an effective amount of the compound of claim 3 and at least one of the following: surfactant, solid or liquid diluent.
 14. An agriculturally suitable composition for controlling the growth of undesired vegetation comprising an effective amount of the compound of claim 4 and at least one of the following: surfactant, solid or liquid diluent.
 15. An agriculturally suitable composition for controlling the growth of undesired growth of undesired vegetation comprising an effective amount of the compound of claim 5 and at least one of the following: surfactant, solid or liquid diluent.
 16. An agriculturally suitable composition for controlling the growth of undesired vegetation comprising an effective amount of the compound of claim 6 and at least one of the following: surfactant, solid or liquid diluent.
 17. An agriculturally suitable composition for controlling the growth of undesired vegetation comprising an effective amount of the compound of claim 7 and at least one of the following: surfactant, solid or liquid diluent.
 18. An agriculturally suitable composition for controlling the growth of undesired vegetation comprising an effective amount of the compound of claim 8 and at least one of the following: surfactant, solid or liquid diluent.
 19. An agriculturally suitable composition for controlling the growth of undesired vegetation comprising an effective amount of the compound of claim 9, and at least one of the following: surfactant, solid or liquid diluent.
 20. An agriculturally suitable composition for controlling the growth of undesired vegetation comprising an effective amount of the compound of claim 10 and at least one of the following: surfactant, solid or liquid diluent.
 21. A method for controlling the growth of undesired vegetation in crops which comprises applying to the locus of the crop to be protected an effective amount of a compound of claim
 1. 22. A method for controlling the growth of undesired vegetation in crops which comprises applying to the locus of the crop to be protected an effective amount of a compound of claim
 2. 23. A method for controlling the growth of undesired vegetation in crops which comprises applying to the locus of the crop to be protected an effective amount of a compound of claim
 3. 24. A method for controlling the growth of undesired vegetation in crops which comprises applying to the locus of the crop to be protected an effective amount of a compound of claim
 4. 25. A method for controlling the growth of undesired vegetation in crops which comprises applying to the locus of the crop to be protected an effective amount of a compound of claim
 5. 26. A method for controlling the growth of undesired vegetation in crops which comprises applying to the locus of the crop to be protected an effective amount of a compound of claim
 6. 27. A method for controlling the growth of undesired vegetation in crops which comprises applying to the locus of the crop to be protected an effective amount of a compound of claim
 7. 28. A method for controlling the growth of undesired vegetation in crops which comprises applying to the locus of the crop to be protected an effective amount of a compound of claim
 8. 29. A method for controlling the growth of undesired vegetation in crops which comprises applying to the locus of the crop to be protected an effective amount of a compound of claim
 9. 30. A method for controlling the growth of undesired vegetation in crops which comprises applying to the locus of the crop to be protected an effective amount of a compound of claim
 10. 31. A method for controlling the growth of undesired vegetation in rice which comprises applying to the locus to be protected an effective amount of a compound of claim 1 of the formula I.
 32. A method for controlling the growth of undesired vegetation in rice which comprises applying to the locus to be protected an effective amount of a compound of claim 5 of Formula I.
 33. A method for controlling the growth of undesired vegetation in rice which comprises applying to the locus to be protected an effective amount of the compound of claim
 6. 34. A method for controlling the growth of undesired vegetation in rice which comprises applying to the locus to be protected an effective amount of the compound of claim
 7. 35. A method for controlling the growth of undesired vegetation in rice which comprises applying to the locus to be protected an effective amount of the compound of claim
 7. 36. A method for controlling the growth of undesired vegetation in rice which comprises applying to the locus to be protected an effective amount of the compound of claim
 10. 